Tailor-Made Luminescent Polymers through Unusual Metallophilic Interaction Arrays Au···Au···Ag···Ag

A novel and efficient strategy for the synthesis of luminescent polymers bearing metallophilic interactions with unprecedented charge sequences has been designed. For this end suitable basic gold units such as [AuR₂]^-, bearing perhalophenyl derivatives, and dinuclear acid silver terpyridine species, [Ag₂(terpy)₂](CF₃SO₃)₂, have been chosen. Their combination originates the polymeric derivatives [{AuR₂}₂Ag₂(terpy)₂]_n (R = C₆F₅, C₆Cl₂F₃) or [{Au(C₆Cl₅)₂}Ag(terpy)]_n. The change of the perhalophenyl group in the gold complex modulates the strength in the metallophilic contacts and, consequently, the polymer arrays and luminescent properties. The X-ray diffraction studies of these derivatives revealed that there are polymers with unusual + + - - + + - - charge sequences for the R = C₆F₅ and C₆Cl₂F₃ species, whereas the more classical + - + - disposition was found for the bulkiest C₆Cl₅ derivative. Their luminescent properties also vary depending on the formation of these polymer arrays, and time-dependent density functional theory calculations were performed to determine the origin of the luminescence.